WO2011131757A1

WO2011131757A1 - Method for preparing a multilayer coating on a substrate surface by means of thermal spraying

Info

Publication number: WO2011131757A1
Application number: PCT/EP2011/056431
Authority: WO
Inventors: Erick Meillot; Romain Vert; Joël TOULC'HOAT; Gilles Mariaux; Armelle Vardelle
Original assignee: Commissariat à l'énergie atomique et aux énergies alternatives; Centre National De La Recherche Scientifique; Universite De Limoges
Priority date: 2010-04-23
Filing date: 2011-04-21
Publication date: 2011-10-27
Also published as: US20130101745A1; FR2959244B1; EP2561110A1; FR2959244A1; ES2641906T3; EP2561110B1

Abstract

The invention relates to a method for creating a multilayer coating on a substrate surface by means of at least one thermal spraying method, wherein according to said method the following consecutive steps are carried out: a) a nanostructured or finely structured first layer of a first material is deposited by means of a liquid thermal spraying method, the substrate surface not undergoing any preparation or activation treatment other than an optional cleaning treatment prior to depositing the nanostructured or finely structured first layer; and b) a microstructured second layer of a second material is deposited onto the nanostructured or finely structured first layer by means of a thermal spraying method. The first layer from step a) is a coupling layer for optimizing the adhesion of the layer from step b) without surface preparation or activation.

Description

METHOD FOR PREPARING A MULTILAYER COATING ON A SURFACE OF A THERMALLY PROJECTED SUBSTRATE SUBSTRATE

DESCRIPTION

TECHNICAL AREA

The invention relates to a method for preparing a coating on a surface of a substrate by at least one thermal spraying method.

More specifically, the invention relates to a method of preparing a multilayer coating adhering to a surface of a substrate by at least one thermal spraying method.

The invention is particularly applicable to the preparation of a ceramic coating (s) thick on a metal substrate.

The technical field of the invention can be defined generally as that of the preparation, manufacture of thermal spray coating.

STATE OF THE PRIOR ART

Thermal spraying is part of dry surface treatment techniques. This technique makes it possible to produce thick coatings, generally of a thickness of a few tens of microns to a few hundred or even thousands of microns, of very varied natures on substrates or parts to be coated equally varied.

All thermal spray systems use a heating device in which is introduced a gas, said throwing gas, used to accelerate, heat and transport to the part to be coated with fine particles, which typically have a micrometric dimension, that is to say generally a size of 5 to 100 micrometers. These fine particles, solid in the initial state, can be in the liquid state, semi-melted, or even solid, after passage in the throwing gas.

These particles are injected into the throwing gas using a carrier gas, said carrier gas. The user must match the amount of movement of the carrier gas and the particles with that of the throwing gas to allow the particles to penetrate well into the throwing gas.

The projection gas, raised to high temperature, is thus an enthalpy and kinetic source which makes it possible to heat the particles to their melting point or beyond, and to communicate a certain speed to them.

In what follows, the term "conventional" methods or more simply "conventional" processes, dry thermal spray processes that use dry micrometric powders as opposed to "liquid channel" processes described below which will nanometric particle suspensions or precursor solutions of these particles.

The particles projected onto the substrate crush and spread in multiple ways according to their speed, their melting state, their temperature, etc.

The accumulation of particles on the substrate makes it possible to produce the coating by stacking these particles.

There are many ways to achieve a thermal spraying deposit but the most common processes used in the industry are the flame-powder projection, the arc-wire projection, the supersonic or hypersonic projection called "HVOF" that is ie "High Velocity Oxy-Fuel" or "HVAF" that is to say "High Velocity Air Fuel", and plasma projection (blown arc or radio frequency).

A description of these methods is made in document [1] and in document [2].

All kinds of substrates can thus be provided with a coating and acquire a reinforced function during their use.

For example, these substrates may be provided with a layer acting as a thermal barrier, or an anti-corrosion barrier, an anti-wear layer, etc., or a layer providing them with properties of thermal stability, hardness, etc.

However, many problems remain, in particular due to an incompatibility between certain thermal spraying techniques and the characteristics of the part to be coated, or between the filler material intended to constitute the coating and the part to be coated.

Thus, some thermal spraying processes do not allow the coating of mechanically fragile parts, whose thermal sensitivity is important, or of complex shape parts. with inaccessible areas.

With the filler material, there are problems of wettability, adhesion, and differential expansion with the material that constitutes the part to be coated.

One of the fundamental properties that thermal spray coatings must exhibit is the adhesion of these coatings to the surface of the part to be coated, also called a substrate.

Different mechanisms of adhesion have been highlighted, these mechanisms are as follows:

the mechanical anchoring: it is generally due to the contraction of the projected material in the roughness of the substrate;

adsorption: This is an adhesion that can generally be described as "chemical" adhesion, which may range from chemisorption due to Van der Waals forces to physisorption due to permanent dipoles.

electrostatic adhesion: it is caused by a double layer of charges of sign opposite to the interface.

diffusion: it may be a molecular diffusion in the case of polymers, or an atomic diffusion in the case of alloys, in the vicinity of the interface.

Several studies have shown that the predominant mechanism in thermal spraying is the mechanical anchoring of the projected particles on the asperities present on the surface of the substrate.

To obtain an increased mechanical adhesion, different methods of surface preparation are used, the most common being shot blasting with different abrasive materials such as sand, corundum and ice as described in documents [5] and [6].

However, during the impact of the abrasive material on the surface, residues remain anchored in the surface and are sources of pollution. This is why the technique of high-pressure water jet ablation has been developed. This technique, which makes it possible to modify the roughness of the surface of the substrate substrate without incorporating abrasive residues, is described in particular in documents [7] and [8].

However, in addition to the possible phenomena of surface contamination, the surface preparation techniques mentioned above require the use of high pressures and therefore induce, depending on the case, compressive or tensile stresses, up to 400 MPa on the surface. of the substrate. These constraints can in the case of substrates of small thicknesses, generate significant deformations.

In order not to deform the substrates by mechanical stresses, other surface preparation techniques have been developed.

Thus, documents [10] and [11] propose the use of a laser irradiation that can result in total or partial removal of the surface contaminating film and a change in the morphology of the surface of the substrate.

Document [12] mentions the use of electrical discharges between an electrode and the substrate to suppress the oxide layers and create roughness.

Various studies, presented in documents [13], [14], and [15] show the influence of other mechanisms of adhesion than mechanical anchoring, relatively complex and uncontrolled.

It appears that the use of the techniques mentioned above, called surface activation, is difficult to envisage industrially for the preparation of a surface prior to thermal spraying because of their high financial cost.

In summary, the industrial or experimental activation or surface preparation techniques described above, which are intended to improve the adhesion of thermally sprayed coatings, have the disadvantage of either a high financial cost or the disadvantage of generating mechanical stresses in the substrate to be coated.

There is therefore a need for a process for preparing a microstructured coating on a substrate by a conventional dry thermal spraying method which provides a coating having excellent adhesion properties, improved, without recourse to to a preparation or activation of the surface of the substrate other than a simple cleaning.

In the early 1990s, a new thermal projection technique was introduced, namely the projection of nanomaterials by liquid ", called suspension projection.

The carrier gas and the micrometric particles of the conventional thermal spray are replaced by a suspension, dispersion or mixture of a liquid and nanoscale particles.

Indeed, in the conventional thermal spray method, dry, the particles must have a sufficient amount of movement to promote their penetration into the projection gas and thus allow adequate heat treatment of these particles.

However, the nanoscale particles, because of their low mass, can not reach sufficient amounts of movement, unless significantly increase the flow of carrier gas, which results in significant deviations of the throwing gas, making impossible any construction of the deposit.

By using a suspension, the implementation of nanometric particles, which were not possible with the "classical" dry process becomes possible.

Indeed, in contact with the projection gas, the jet of particles in suspension will fragment, and the liquid will evaporate, the particles will therefore be heat treated and accelerated to the part to be coated, to form a coating finely structured, as described in document [16].

Document [17] describes a system for producing plasma sputter deposits from suspended nanoparticles. The thermal projection of suspensions is also the subject of documents [18], [19], and [20].

Further studies have determined the process parameters that influence the deposition construction ([21], [22]) and the possible cohesion with the substrate ([23], [24], [25]).

The nanostructured layers have optimized properties, both mechanical and ^{physico¬chemical} . Indeed, a decrease in the size of the particles makes it possible to greatly increase their specific surface area, the number of interparticle contacts as well as the shape, the size and the geometry of the porosities.

Due to the decrease in the size of the particles used in the suspension thermal spraying process, new phenomena have to be taken into account.

Thus, the mechanical attachment requires surface roughness of a much smaller size, namely submicron or even nanometric sizes, and new adhesion mechanisms appear, such as Van der Waals forces or electrostatic forces.

Coatings prepared by thermal spraying of suspensions do not require any special surface preparation.

The document [26] shows that it is possible to make deposits with optimized properties and significant thickness (100 ym). However, an excessive increase in the thickness of the nanostructured deposit can lead to its decoherence [27].

The thermal projection of suspensions is therefore limited to the production of so-called "thin" layers, namely of a thickness generally less than 150 microns.

Liquid thermal spraying methods therefore allow the preparation of adherent layers, but they are only nanostructured or finely structured and non-microstructured layers that are thin.

The need, already mentioned above, for a process for preparing a microstructured coating on a substrate by a thermal spraying process which makes it possible to obtain a coating having excellent adhesion properties, improved, without resorting to a preparation or activation of the surface of the substrate other than a simple cleaning, remains intact.

In other words, there is therefore, in view of the above, a need for a process for preparing a coating on a substrate by thermal spraying, which does not have the disadvantages, defects, limitations and disadvantages of the processes of the prior art such as conventional dry processes and that solves the problems of these methods.

The object of the present invention is to provide such a method that meets this need, among others.

STATEMENT OF THE INVENTION

This and other objects are achieved according to the invention by a method of preparing a multilayer coating on a surface of a substrate by at least one thermal spraying method, in which the following successive steps are carried out:

a) depositing on the surface of the substrate a first nanostructured or finely structured layer of a first material by a liquid thermal spraying method; the surface of the substrate having undergone, prior to the deposition of the first nanostructured or finely structured layer, no preparation or activation treatment other than a possible cleaning treatment;

b) depositing on the first nanostructured or finely structured layer a second microstructured layer of a second material by a thermal spraying method.

Cleaning also means degreasing. Advantageously, the coating is a thick coating.

Thick coating, within the meaning of the invention, generally means that the coating has a thickness greater than or equal to 100 μm, preferably greater than or equal to 150 μm.

The thickness of the coating, which is generally greater than or equal to 100 μm, preferably greater than or equal to 150 μm, can generally be up to 1 mm or even 10 mm, and this thickness is equivalent to that of a deposit obtained by a conventional projection method in which a preparation, activation of the surface is carried out for example by mechanical sanding.

In other words, in the process according to the invention is generally a deposit of a "thick" coating of a thickness that can be described as conventional, with the difference that it does not achieve any preparation of the surface of the substrate to increase the roughness and that in order to maintain a good adhesion, it is first possible to deposit a nanostructured or finely structured first layer by a liquid route.

The thermal spraying method implemented in step b) can be any method.

However, advantageously, the thermal spraying method of step b) may be a dry thermal spraying method.

Advantageously, during step a), the thermal spraying method may use a suspension of nanometric or submicron particles of the first material.

By nanometric particles, it is generally understood that these particles have a size, generally defined by their largest dimension, of 1 to 100 nm.

By submicron particles, it is generally understood that these particles have a size, generally defined by their largest dimension, of more than 100 nm to 1000 nm.

These nanometric or submicron particles whose size is therefore generally in the range of one hundred nanometers can not be projected by a conventional dry process, but only by a liquid process.

These nanoscale particles or Sub-microns are then processed, whereby the nanoscale or submicron particles form the first nanostructured or finely structured layer of the first material on the surface of the substrate.

Or, in step a), the thermal spraying method uses a solution of precursor reagents of the first material.

This solution of precursor reagents is then treated with an enthalpy source, whereby the precursor reactants react and form the first nanostructured or finely structured layer of the first material on the surface of the substrate.

Advantageously, the thickness of the first nanostructured or finely structured layer of the first material deposited on the surface of the substrate may be greater than the thickness of said first layer in the final multilayer coating obtained at the end of the process.

Advantageously, during step b) the thermal spraying method uses a dry powder of micron micron particles, of the second material, and these micron particles are then treated, whereby the micron particles form the second microstructured layer of the second material on the first layer.

Advantageously, the second material has the same composition as the first material (in other words, the first material and the second material are the same) and / or the second material has a crystallographic structure close to that of the first material, and / or the second material behaves thermomechanical close to that of the first material.

In other words, advantageously, the nanostructured layer has the same (chemical) composition as the microstructured layer.

In other words, advantageously, the nanostructured layer and the microstructured layer are in the same material and differ in that one has a nanostructure while the other has a microstructure.

Advantageously, after step b), a step c) is carried out during which a third microstructured or nanostructured or finely structured layer of a third material is deposited on the second microstructured layer of the second material by a thermal spraying method.

The thermal spraying method for the deposition of the third layer may be a thermal spray method dry or liquid.

The third layer may indeed be microstructured or nanostructured or finely structured depending on the intended application. Thus, a third nanostructured or finely structured layer is preferred, for example, in the case where it is desired to provide a seal to the coating.

The second and third layers of steps b) and c) can have different functions.

Advantageously, the third material has the same composition as the second material (in other words, the third material and the second material are the same) and / or the third material has an crystallographic structure close to that of the second material, and / or the third material has a thermomechanical behavior close to that of the second material.

In other words, advantageously, the third layer has the same (chemical) composition as the second layer.

In other words, advantageously, the third layer and the second layer are made of the same material.

Advantageously, the liquid thermal spray method used in step a) is chosen from supersonic or hypersonic projection processes called "HVOF" that is to say "High Velocity Oxy-Fuel" or "HVAF" c. 'High Velocity Air Fuel', the detonation gun projection process known as the 'D-GUN' process, and the plasma spraying processes, for example by blown arc or radio-frequency plasma.

Advantageously, the thermal spraying method used in step b) is a dry thermal spraying method chosen from the processes used for step a), namely the supersonic or hypersonic projection processes called "HVOF". that is to say "High Velocity Oxy-Fuel" or "HVAF", that is to say "High Velocity Air Fuel", the method of projection by detonation gun called "D-GUN" method, and the methods of plasma projection, for example by blown arc plasma or radio frequency; and, further, among the flame-powder projection method, and the arc-wire projection method. Advantageously, the thermal spraying method used in step c) is either a liquid thermal spraying method chosen from the liquid thermal spraying methods used for step a), namely the supersonic or sputtering projection methods. hypersonic called "HVOF" that is to say "High Velocity Oxy-Fuel" or "HVAF" that is to say "High Velocity Air Fuel", the method of projection by detonation gun called process "D- GUN ", and plasma projection methods, for example by blown arc or radio-frequency plasma, in the case where the layer deposited in step c) is a nanostructured or finely structured layer; or a dry thermal spray method chosen from the dry thermal spray methods used for step b), namely the supersonic or hypersonic projection processes called "HVOF", that is to say "High Velocity Oxy-Fuel "or" HVAF "that is to say" High Velocity Air Fuel ", the method of projection by detonation gun called" D-GUN "method, and plasma projection methods, for example by blown arc or radio-frequency plasma, and, in addition, among the flame-powder projection method, and the arc-wire projection method in the case where the layer deposited in step c) is a microstructured layer .

Advantageously, prior to step a), the substrate is preheated and / or before step b) the first layer is preheated.

Advantageously, the first, second and third materials are chosen independently of each other from among the ceramics, preferably the ceramics oxides, metals, and cermets.

Advantageously, the first and second materials, and possibly the third material, are a single ceramic, preferably an oxide ceramic, such as Yttrine stabilized zirconia, YSZ.

Advantageously, the substrate is made of a material chosen from metals and metal alloys.

These metal alloys may be chosen especially from steels, preferably from stainless steels.

Advantageously, the first and the second material, and possibly the third material, are the same ceramic, preferably the same oxide ceramic, such as yttrine-stabilized zirconia (YSZ), and the substrate is a substrate made of a metal or in a metal alloy, preferably a steel substrate, for example a stainless steel substrate.

The method according to the invention has a specific sequence of specific steps which has never been described or suggested in the prior art, represented in particular by the documents cited above.

The method according to the invention can be defined as a process in which a first nanostructured or finely structured layer is prepared by thermal spraying, generally by liquid thermal spraying, and this nanostructured or finely structured layer is used as an adhesion layer for a microstructured layer also prepared by thermal spraying, generally by conventional thermal spray, dry. Finally, a coating generally prepared by thermal spraying and having excellent adhesion to the substrate is finally obtained.

Surprisingly, in this way, thanks to the process according to the invention, an excellent adhesion of the microstructured layer to the substrate, not previously prepared, is obtained even though until then, it was necessary to obtain such adhesion of use a mechanical anchoring of this microstructured layer on the substrate.

In particular, it is generally no longer necessary, with the method according to the invention to carry out a preliminary preparation of the surface of the substrate, such as sandblasting, in order to increase the surface roughness to promote mechanical anchoring of a substrate. coating and in particular a thick coating.

More generally, it is not necessary with the method according to the invention to implement a preparation or prior activation of the surface of any substrate. In other words, there is no change in the surface condition of the part in the process according to the invention, the substrate to be coated prior to the deposition of the first layer.

The process according to the invention makes it possible to prepare coatings, in particular coatings which are thick and which have excellent adhesion to substrates by thermal spraying, without recourse to surface preparation or activation, other than a simple cleaning of the surface of the surface. substrate.

By obtaining excellent adhesion of a microstructured layer and a coating, in particular of a thick coating, prepared by thermal spraying on a substrate, although, surprisingly, a preparation or activation treatment of the substrate is not previously carried out, the process according to the invention goes against the prejudice that a preparation or activation of the surface of the substrate was necessary to obtain the adhesion of such microstructured layers and such coatings especially such thick coatings on a substrate.

The coatings prepared by the process according to the invention, the adhesion of which is improved compared with the microstructured coatings prepared on substrates which have undergone activation or surface preparation, do not have, moreover, all the drawbacks associated with these preparatory treatments. and activating the surface of the substrate particularly in terms of financial cost and mechanical constraints.

In summary, the process according to the invention makes it possible for the first time to prepare a thick and adherent coating on a surface of a substrate by a thermal spraying process without any preparation or activation of this surface except for a simple cleaning. The method according to the invention thus overcomes all the problems of adhesion related to the nature and / or the roughness of the surfaces to be coated, it is of very general application and ensures excellent adhesion of the coating whatever the nature of the surface of the substrate, the state of this surface defined in particular by its roughness, shape, geometry of this surface, even complex, and the size of this surface.

The process according to the invention does not have the disadvantages of the processes of the prior art and overcomes the problems of the processes of the prior art. Indeed, it does not have the drawbacks of the coating preparation processes by conventional dry processes in that it ensures excellent adhesion of the essentially microstructured coating to the substrate without activation or prior preparation.

Compared to liquid spray preparation methods, the process according to the invention makes it possible to prepare cohesive and thick coatings which was not possible with this type of process.

In other words, the method according to the invention consists inter alia of:

to create a coating, in particular a thick ceramic coating adapted to the industrial needs strongly adherent on a piece in particular a metal part;

creating a coating, in particular a ceramic coating without prior surface preparation;

using a highly adherent nanostructured or finely structured layer in a deposition layer, preferably a microstructured "conventional" deposit, to thereby create adhesion via a multilayer system.

The process according to the invention makes it possible inter alia: to control the thickness of the final coating which can range from a few hundred nanometers to a few millimeters, for example from 1 mm to 5 mm.

to be able to produce coatings on pieces of complex shapes and of various sizes.

The process according to the invention can be industrialized rapidly and with a lower production cost than the processes of the prior art.

It may be noted that nanostructured or finely structured layers prepared by thermal spraying, have never been used as surface preparation and attachment layers prior to a "classical" microstructured layer also prepared by thermal spraying.

According to the invention, it has been demonstrated that these nanostructured layers that allow, via a multilayer system, to optimize the adhesion of a more or less thick coating on a surface that has not been previously prepared and thus to simplify the projection procedures.

The use of dual or multilayer systems to optimize adhesion, with prior surface preparation, has certainly been the subject of various studies, particularly in aeronautics and aerospace as indicated in document [28].

But this use is limited to systems using microstructured metal sub-layers, for example NiCrAlY type. In addition, these microstructured layers are made, with initial sandblasting, by projection methods which are not liquid projection processes involving the projection of suspensions or solutions.

In fact, the problems of adherence of a ceramic to a metal are not new and are largely due to the stresses resulting from the differences in coefficient of thermal expansion between the substrate and the coating.

For this, the use of a multi-layer system, with a NiCrAlY type metal sub-layer, makes it possible to create a coefficient of thermal expansion gradient between the substrate and the last functional layer of the coating, and thus to limit these mechanical stresses [ 32], [33] [34], [35], [36], [37]. Nevertheless, the adhesion is always of mechanical origin and the substrates always require a preparation in order to have the high roughness necessary for the adhesion of microstructured layers of great thickness [38], [39], [40], [41] , [42].

It is also possible to find various coating techniques using nanostructured multilayer systems to promote adhesion [43], [44], [45]. But all these techniques, such as physical vapor deposition ("PVD"), physical vapor deposition electron beam ("EB-PVD"), chemical vapor deposition ("CVD"), and plasma enhanced chemical vapor deposition ("PECVD"), are complex and require surface preparation, for example a polished surface, a high vacuum (about 10 ^{~ 5} mbar) [46] and are applicable only for thin layers. It is therefore essential to have equipment and a specific environment, which leads to limiting the size and shape of the parts to be coated and considerably increases the cost of production.

It should be noted that up to now, the superposition of a nanostructured layer and a microstructured layer, the nanostructured layer acting as a tie layer of a microstructured layer, has never been realized in order to improve adhesion while preferably keeping the same chemical composition of the two layers.

The invention will be better understood on reading the following detailed description made in particular with reference to preferred embodiments of the method of the invention, this description being given for illustrative and not limiting.

BRIEF DESCRIPTION OF THE DRAWINGS

The detailed description is made with reference to the accompanying drawings, in which:

- Figure 1 is a schematic view showing a thermal spraying device for implementing the method according to the invention;

Figure 2 is a schematic cross-sectional view of a coating, system, bilayer prepared by the method according to the invention, on a substrate, substrate;

Figure 3 is a schematic vertical sectional view of a coating, system, trilayer prepared by the method according to the invention, on a substrate, substrate;

Figure 4 is an image obtained by scanning electron microscopy which shows the microstructure obtained in the example by the method according to the invention.

DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS

The process according to the invention can be described as a process for the preparation of a multi-layer, multimodal coating by thermal spraying onto a surface of a substrate, also called a substrate, to be coated. The thermal spraying can be carried out under a normal atmosphere, controlled, for example inert or neutral, or low pressure, that is to say under a pressure of a few millibars.

By multimodal system is meant that the coating system comprises at least two layers that are different in structure, structural scale, and organization. Thus, the first layer is a nanostructured or finely structured layer, while the second layer is a microstructured layer.

By nanostructured layer, or finely structured, it is generally understood that this layer has an organization at the nanoscale, that is to say on a scale ranging from one or a few nanometers up to a few hundred nanometers. Similarly, microstructured layer means that this layer has an organization at the micrometer scale, that is to say on a scale ranging from one or a few microns to a few hundred micrometers.

Each of the layers of the process according to the invention may be deposited by a different thermal spraying method and with the aid of a thermal spraying device different, but it is advantageous to perform the deposition of all layers including the first and second layers with the same method and the same thermal spraying device.

This device should preferably be easily adapted to perform either the projection of micrometric powders of materials, such as ceramics, by the conventional or dry route, or the projection of suspensions of micron powders of materials such as ceramics, by the liquid pathway, is still the projection of reagent solutions capable of forming after treatment with an enthalpy source, a nanostructured or finely structured deposition.

The thermal projection method implemented by the device may be of any nature whatsoever and may be chosen in particular from the thermal projection methods already mentioned above, namely the flame-powder projection, the arc-wire projection, the supersonic or hypersonic projection called "HVOF" that is to say "High Velocity Oxy-Fuel" or "HVAF" that is to say "High Velocity Air Fuel", and plasma projection, according to their adaptability to the dry way and the liquid way.

Among these methods, those skilled in the art easily identify those that can be implemented by the dry route and those that can be implemented by a liquid route.

The choice of thermal spraying method depends on the melting temperatures of the material to be projecting and substrate material material, substrate to be coated. Advantageously, this device can be placed on a robot arm in order to scan the entire surface of the substrate, of the part to be coated, to thereby uniformize the multilayer coating.

The size, shape and geometry of the substrate, the part and the substrate to be coated by the process according to the invention may be arbitrary. This is indeed one of the advantages of the method according to the invention to allow the preparation of an adherent coating on all kinds of parts regardless of their shape, size and geometry, even complex. In fact, the only limit that can be encountered in the implementation of the invention lies in the mechanical positioning capabilities of the robot and is not due to the characteristics of the process as such.

A device for implementing the method according to the invention is shown in FIG. 1; for simplification purposes the robot arm which is generally provided with the device has been omitted in FIG.

This thermal spraying device firstly comprises a device for injecting and accelerating the particles (1) which also acts as an enthalpy source.

The device (1) varies according to the thermal spraying method used. In this regard, reference may be made to documents [1], [2] or [17].

The thermal spraying device then comprises a feed system (2) for coating materials which may be either in the form of dry powders in the case where the conventional or dry route is used, or in the form of suspensions of these powders or in the form of precursor reagent solutions in the case where the liquid channel is used.

FIG. 1 also shows the trajectory (3) of the melted, semi-melted or solid particles in flight which are deposited on the substrate to be coated (4).

The substrate (4) can be of a material selected from metals and metal alloys such as for example steel, alloys based on nickel, alloys such as Haynes ^® available under the name, the inconels ....

Prior to the deposition of the first layer of a first material on the substrate surface, which is to be coated, this surface is generally cleaned, for example degreased with a solvent, this is a conventional industrial process.

According to the method according to the invention, the surface of the substrate undergoes no activation treatment or preparation other than this possible cleaning treatment, for example degreasing. This cleaning treatment in no way affects the structure or composition of the surface of the substrate, ie the surface condition of the substrate and is intended to remove impurities, pollutants and other foreign matter on the surface of the substrate which are distinct from it and do not belong to it.

The surface of the substrate can optionally be qualified as a "smooth" and "clean" surface.

This surface does not offer the possibility of mechanical anchoring on the scale of a microstructured layer.

The substrate may be optionally preheated, prior to deposition by any suitable means, at a temperature of, for example, 25 to 600 ° C.

The preheating temperature depends on the properties of the coating materials and substrates.

This preheating step allows improved adhesion between the substrate (4) and the first layer of the coating.

Following this optional preheating step, the surface of the substrate is coated with a first nanostructured or finely structured layer of a first material by a liquid thermal spraying method.

The liquid process which is implemented for the deposition of the first layer of the coating may use nanometric particles (nanoparticles) or even submicron particles of the first material, in suspension, which are then treated in a known manner, according to the projection method. chosen, and form the first nanostructured or finely structured layer (21) at the surface of the substrate (20), as shown in FIG.

Any projection method capable of projecting nanometric powders in suspension can be used for the deposition of the first layer or attachment layer. The Prosol ^® process which is described in particular in the patent application [17], the description of which we can refer to, is a method likely to be suitable for the deposition of the first nanostructured layer or finely structured.

The nanoparticles or nanoscale particles generally have a size of 1 to 500 nm, preferably 1 to 100 nm, more preferably 1 to 50 nm.

The submicron particles generally have a size of 200 nm to 1 μm, preferably 200 to 800 nm. Or, the method which is implemented for the deposition of the first layer uses a solution of precursor reagents of the first material which is treated in a known manner by a process-specific enthalpic source and can react and form a deposit (21). ) also nanostructured surface of the substrate (20) of the same composition as the first material deposited by projection of a suspension.

The projection parameters will be adapted to the first material to be projected.

The first material which constitutes the first layer (21) of the coating prepared by the process according to the invention is generally chosen from ceramics, preferably from metal oxide (s), such as zirconia, alumina, silica, hafnium oxide (hafnine), titanium dioxide, etc.

In the case where a solution of precursor reagents of the first material is used, the reactants are generally chosen from metal salts and metal alkoxides.

When preparing the first layer (21) or connecting layer, the projection atmosphere or more precisely, the atmosphere in which the projection is performed is not necessarily oxidizing because the oxidation of the particles in flight is not necessary.

The first nanostructured or finely structured layer (21) of the first material, is strongly adherent, and serves as a bonding layer and attachment to the upper layers and firstly to the second layer constituted by a second material.

This first layer may thus be called "nanostructured bond layer" (21).

This first layer has a nanostructuring that is to say that it is structured at the nanoscale. Thus, if we project for example spherical particles having for example a diameter of 500 nm, these particles during their impact on the substrate will collapse, flatten to give slats with a thickness of 20 to 30 nm. We will therefore obtain a layer consisting of a stack of thin strips that overlap to form a finely structured deposit with a nanoporosity or porosity at the nanoscale.

The thickness of this first layer (21) depends on the material to be sprayed. This thickness can generally range from one to a few ym to less than 150 μm (in terms of deposited thickness).

In other words, the thickness of the first layer can be up to 150 μm, the value 150 μm being excluded.

Indeed, it is preferable that the thickness of the first layer (21) which is a nanostructured or finely structured layer, ie less than 150 μm, because for greater thicknesses the coherence of this layer is not ensured.

Preferably, the deposited thickness of the first layer (21) is from 1 μm to 100 μm.

Advantageously, this first layer (21) may have a thickness greater than its nominal thickness of function (that is to say its thickness in the multilayer final coating obtained at the end of the deposition of all the layers). ablation that can occur with the realization of the second layer.

Thus, if it is desired that the nominal thickness of function of the first layer is from 1 to 100 μm, the thickness of the initially deposited layer before deposition of the second layer may be from 1 to 150 μm.

Following the deposition on the substrate surface of the first layer (21) of the first material, depositing on this first layer, a second microstructured layer (22) of a second material by a thermal spraying method.

No preparation, activation of the first layer is required before proceeding with the deposition of the second layer.

The first layer (21) may be optionally preheated, prior to the deposition of the second layer (22), by any suitable means, for example at a temperature of 25 to 600 ° C.

This preheating step allows improved adhesion between the first layer and the second layer of the coating, especially when it is two layers of ceramics.

Any thermal spraying process for the preparation of a microstructured layer may be used.

This second microstructured layer is generally deposited by a "conventional" thermal spray method by the dry route.

The projection method which is implemented for the deposition of the second layer of the coating uses a dry powder of micrometric particles of the second material, which are projected on the surface of the substrate, and form in known manner the second microstructured layer (22). at the surface of the first nanostructured or finely structured layer (21).

The micrometric particles or microparticles generally have a size of 5 to 150 μm, preferably 10 to 20 μm, or 20 to 60 μm depending on the type of process used.

The second material which constitutes the second microstructured layer (22) generally has the same composition as the first material, or the second material has a crystallographic structure close to that of the first material, or the second material has a thermomechanical behavior close to that of the first material. material. By thus choosing the first material of the nanometric or finely structured layer (21) and the second material of the micrometric layer (22), a maximum of cohesion is ensured between the two layers.

In other words, according to the invention, the same material for the layer is preferably used. link (21) and for the upper layer (22).

The materials of these layers are therefore preferably identical.

This homogeneity in the composition of the different layers is one of the additional advantages provided by the method according to the invention in this preferred embodiment.

Because of the homogeneity of the composition of the layers, the control of the cohesion of the layers does not require the control of the oxidation, especially on the surface of the bonding layer (21).

In other words, there is no oxidation problem at the interface between the layers when, advantageously, the two layers are of identical composition.

When the material of the first layer advantageously has the same composition as the material of the second layer, there is no composition gradient in the coating.

The second material which constitutes the second layer of the coating prepared by the process according to the invention is, like the first material, generally chosen from ceramics, preferably from metal oxide (s), such as zirconia, alumina, silica, hafnium oxide (hafnine), titanium dioxide, etc., these particles can be dense or porous.

The projection parameters of the thermal spraying method implemented for the deposition of the second layer will also be adapted to the second material (22).

The thickness of the second layer depends usually the function of this layer.

The thickness of the second layer may range from 10 μm to 5 mm, preferably from 10 to 1000 μm.

Thus, according to the invention, microstructured thick layers can be prepared on a substrate by obtaining excellent adhesion thereto and without any activation or preparation treatment of the substrate or of the first layer being carried out.

The adhesion between the first and second layers (21, 22) occurs chemically and is the result of the thermokinetic state of the particles of the second layer (22) which is related to the projection parameters. This adhesion is also achieved by penetration of the particles of the second material in the layer (21), and thus by mechanical anchoring.

It should be noted, moreover, that no post-treatment, that is to say no post-deposit treatment, is generally necessary between the layers and on the final coating.

In other words, no post-treatment is generally carried out on the first layer after its deposition, nor on the second layer after its deposition.

In order to better control the structural and therefore physicochemical properties of the multilayer system, it is possible to deposit an additional layer or third layer (23), as shown in FIG. 3. This third layer may be called an adjustment layer. properties of the multilayer.

This layer can be nanostructured or finely structured or microstructured, the two lower layers serving as a layer of adhesion to this third layer.

The third material that constitutes this layer (23) may be identical in composition to the second material or crystallographic structure close to that of the second material, or thermomechanical behavior close to that of the second material, especially according to industrial needs. By thus choosing the second material of the micrometric layer (22) and the third material of the layer (23), a maximum of cohesion is ensured between the two layers (22) and (23).

In other words, advantageously, the second layer and the third layer are made of the same material.

The advantages provided by the choice of a third material having a composition identical to the second material are similar to those obtained by choosing a second material having a composition identical to the first material and have already been exposed above. In particular, when the third material is identical to the second material, there are no oxidation problems between the second and third layers.

Advantageously, the first material, the second material and the third material all have an identical composition, the same composition (chemical).

In other words, advantageously, the three layers are made of the same material, for example in one even ceramic.

When the material of the three layers advantageously has the same composition, there is no composition gradient in the coating.

The third material which constitutes the third layer (23) of the coating prepared by the process according to the invention is, as well as the first material and the second material, generally chosen from ceramics, preferably from metal oxide (s), such as zirconia, alumina, silica, hafnium oxide (hafnine), titanium dioxide etc., these particles can be dense or porous.

This third layer (23), when it is a microstructured layer, is generally deposited by a "conventional" thermal spray method by the dry route in a similar manner to the second layer (22).

This third layer (23), when it is a nanostructured or finely structured layer, is generally deposited by a liquid thermal spraying method similarly to the first layer (21).

The projection parameters of the thermal spraying method implemented for the deposition of the second layer will also be adapted to the third material (23).

The thickness of the third layer generally depends on the function of this layer.

The thickness of the third layer may range from 10 μm to 5 mm, preferably from 10 μm to 1 mm in the case of a microstructured layer, and from 1 μm to 100 μm, preferably from 10 μm to 60 μm, in the case of a microstructured layer. the case of a nanostructured or finely structured layer.

The second layer (22) and the third layer (23) of the coating generally have properties of different functions.

Thus, the second layer (22) can be defined as a functional layer that will impart improved function to the coated substrate part. For example, this second layer (22) may be a thermal barrier or electrical barrier layer.

The third layer (23) which, as we have seen, can be defined as a layer of adjustment of the properties of the multilayer coating, is the outer layer which provides the coating with essential properties vis-à-vis the environment.

For example, the third layer can give external gas tightness properties, anti-corrosion properties (eg against acids), anti-wear properties, thermal barrier properties. In particular, if the third layer is a nanostructured or finely structured layer, it will have less porosity, and it will therefore be more tight especially with respect to gases.

Note, again, that no post ^¬ treatment is generally required between the three layers and the final coating.

In other words, no post-treatment is generally carried out on the second layer, after its deposition, or on the third layer, after its deposition.

The process according to the invention makes it possible to prepare coatings which have variable thicknesses, but it proves to be particularly advantageous for the preparation of thick coatings, that is to say generally of a thickness greater than or equal to 100 μm, preferably of a thickness greater than or equal to 150 μm, which, thanks to the process according to the invention, exhibit excellent adhesion and excellent cohesion.

The final coating which is essentially a micrometric microstructured coating, thus has a thickness generally of 100 μm to 10 mm, preferably 150 μm to 10 mm, more preferably 150 μm to 1 mm.

Such a coating finds particular application in the aeronautical, space, naval, and nuclear industries.

It has been shown above that the invention makes use of the use of a first nanostructured or finely structured layer produced by thermal spraying as an adhesion layer for coatings, preferably thick coatings conventionally produced by thermal spraying and usually requiring mechanical adhesion. It is no longer necessary to perform preliminary preparation to increase the surface roughness to promote mechanical anchoring of a thick coating.

The process according to the invention is not limited to the preparation of thermal barriers but may be suitable for the preparation of any coating.

The invention will now be described with reference to the following example, given by way of illustration and not limitation. EXAMPLE:

This example illustrates the realization of a two-layer system on an AISI 304L 50x50 mm ² raw machining substrate (R _a ~ 0.5 μm):

Step 1: Cleaning the sample

• Acetone bath (30 minutes).

• Ethanol bath activated with ultrasound.

Step 2: Realization of the layer Ci (21)

Nanostructured coating of YSZ (zirconia stabilized with yttrine) made by liquid plasma projection:

· Size of suspended particles:

30-60 nm.

• Suspension load rate: 6% by weight.

• Flow rate of suspension: 70 g / min.

· Plasma torch type: Sulzer-Metco ^® , type F4.

• Torch / substrate relative speed:

1.5 m / s.

• Projection distance: 40 mm.

· Plasma mixture and gas flow rate used: Ar / He / H ₂ , 45/45/3 NL / min.

• Useful power of the torch: ~ 28 kW.

• Preheating temperature of the substrate: 250 ° C.

· Duration of the projection: 15 min. Step 3: Realization of the layer C _Σ (22) YSZ microstructured coating (zirconia stabilized with yttrine) made by conventional plasma projection (dry process):

• Particle size: 22-45 ym.

• Chemical composition of the powder: same layer Ci (21).

• Powder flow rate: 20 g / min.

• Projection distance: 150 mm.

• Plasma mixture: Ar / He / H2.

• Preheating temperature of the layer Ci: 250 ° C.

• Projection time: 10 min.

The thickness of the first layer Ci (21) is about 20 μιη, and the total thickness of the coating is about 350 to 360 μιη, for example 354 μιη or 363 μιη as shown in FIG. the microstructure obtained:

Figure 4 is a scanning electron microscope image showing the different layers deposited as described above on the substrate.

We see in the photograph of the

Figure 4 that the interface between the first layer Ci (21) and the second layer C2 (22) is barely visible, which shows that the consistency between these two layers is excellent. REFERENCES

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Claims

A process for preparing a multilayer coating on a surface of a substrate (20) by at least one thermal spraying method, wherein the following steps are carried out:

a) depositing on the surface of the substrate (20) a nanostructured or finely structured first layer (21) of a first material by a liquid thermal spraying method; the surface of the substrate (20) having undergone, prior to the deposition of the first nanostructured or finely structured layer (21), no preparation or activation treatment other than a possible cleaning treatment;

b) depositing on the nanostructured or finely structured first layer (21) a second microstructured layer (22) of a second material by a thermal spraying method.

2. The method of claim 1, wherein the coating is a thick coating of a thickness greater than or equal to 100 μm, preferably of a thickness greater than or equal to 150 μm.

3. A method according to any one of the preceding claims, wherein the thermal spraying method of step b) is a dry thermal spraying method.

4. Method according to claim 1, wherein, in step a), the projection method thermal uses a suspension of nanoscale or submicron particles of the first material.

5. The method of claim 1, wherein, in step a), the thermal spraying method uses a solution of precursor reagents of the first material.

6. A method according to any one of the preceding claims, wherein the thickness of the first nanostructured or finely structured layer of the first material deposited on the surface of the substrate is greater than the thickness of said first layer in the final multilayer coating obtained. at the end of the process.

7. The method of claim 3, wherein in step b) the thermal spraying method uses a dry powder of micrometric particles of the second material.

The method according to any one of the preceding claims, wherein the second material has the same composition as the first material and / or the second material has a crystallographic structure close to that of the first material, and / or the second material has a thermomechanical behavior close to that of the first material.

9. Process according to any one of the preceding claims, in which after step b) a step c) is carried out during which one depositing a third microstructured or nanostructured or finely structured layer (23) of a third material on the second microstructured layer (22) of the second material by a thermal spraying method.

The method according to claim 9, wherein the third material has the same composition as the second material and / or the third material has a crystallographic structure close to that of the second material, and / or the third material has a thermomechanical behavior close to that of the second material.

11. Process according to any one of the preceding claims, in which the liquid thermal spraying method used in step a) is chosen from supersonic or hypersonic projection processes called "HVOF", that is to say "High Velocity Oxy-Fuel" or "HVAF" ie "High Velocity Air Fuel", the method of projection by detonation gun called "D-GUN" method, and plasma projection methods, by example by blown arc plasma or radio frequency.

The method according to any one of the preceding claims, wherein the thermal spraying method used in step b) is a dry thermal spraying method selected from the processes used for step a), namely the supersonic or hypersonic projection processes referred to as "HVOF", that is "High Velocity Oxy- Fuel "or" HVAF "that is to say" High Velocity Air Fuel ", the method of projection by detonation gun called" D-GUN "method, and plasma projection methods, for example by plasma of blown arc or radio frequency; and, further, among the flame-powder projection method, and the arc-wire projection method.

The method according to any one of the preceding claims, wherein the thermal spraying method used in step c) is either a liquid thermal spraying method selected from the liquid thermal spraying methods used for the spraying process. step a), namely the supersonic or hypersonic projection methods called "HVOF" that is to say "High Velocity Oxy-Fuel" or "HVAF" that is to say "High Velocity Air Fuel", the method of projection by detonation gun called "D-GUN" method, and plasma projection methods, for example by blown arc or radio-frequency plasma, in the case where the layer deposited in step c) is a nanostructured or finely structured layer; or a dry thermal spray method chosen from the dry thermal spray methods used for step b), namely the supersonic or hypersonic projection processes called "HVOF", that is to say "High Velocity Oxy-Fuel "or" HVAF "that is to say" High Velocity Air Fuel ", the method of projection by detonation gun called" D-GUN "method, and plasma projection methods, for example by arc plasma blown or radio- frequency; and furthermore among the flame-powder projection method, and the arc-wire projection method, in the case where the layer deposited in step c) is a microstructured layer.

14. Method according to any one of the preceding claims, wherein prior to step a) preheating the substrate and / or prior to step b), the first layer is preheated.

15. Process according to any one of the preceding claims, in which the first, second and third materials are chosen independently of one another, from ceramics, preferably oxide ceramics, metals and cermets.

16. A method according to any one of the preceding claims, wherein the substrate is of a material selected from metals and metal alloys.